共价有机骨架聚合物功能膜制备方法的研究进展

doi:10.16085/j.issn.1000-6613.2020-1830

摘要/Abstract

摘要：

共价有机骨架聚合物（COFs）是由共价键连接，经热力学可逆聚合形成的有序多孔有机晶态材料，具有比表面积大、孔分布规则可调和可拆剪等特性，其二维或三维COFs功能膜在气体分离、化学传感、催化、药物传输等方面具有广阔的发展前景。COFs膜材料的制备决定膜组成、微规整结构和性能，成为COFs膜功能应用的研究基础和技术关键。本文综述了COFs材料提出以来形成的共混法、原位聚合法、层层堆叠法和界面聚合等制备方法的研究现状，结合各方法优缺点，分析并提出COFs膜制备技术的关键方向和技术要点。为COFs功能膜分子设计、优化和功能化应用提供合理的制备方法，促进高性能COFs功能膜实用化制备方法的形成。

关键词: 共价有机骨架聚合物膜, 共混法, 原位聚合法, 层层堆叠法, 界面聚合

Abstract:

Covalent organic framework polymers (COFs) connected by covalent bonds are ordered porous organic crystals prepared by reversible thermodynamic polymerization. With the characteristics of large specific surface area, adjustable regular pore distribution and detachable structure, COFs functional membranes with two dimensions or three dimensions have been promising in gas separations, chemical sensors, catalysts, drug delivery, etc. The molecule compositions, micro-structures, and performances of COFs membranes are determined by their preparation methodology, which has been a research basis and a key technology for the application of COFs functional membranes. In this paper, recent developments and promising trends of preparing COFs functional membranes, including blending method of COF, in-situ polymerization method, exfoliation and assembly method and interfacial polymerization method, were reviewed and the merits and limitations of each preparation method were analyzed. The research direction and key technical points of each technology in fabricating COFs functional membranes were summarized, and the reasonable preparation methods from the molecule design, functional optimization and potential applications were proposed to promote the formation of preparation methods of high performance COFs membranes in the future.

Key words: covalent organic framework polymer (COFs) membranes, blending method, in-situ polymerization, layer by layer stacking method, interfacial polymerization

中图分类号:

TB383

刘祎, 汪明旺, 吕宏凌, 陈金庆. 共价有机骨架聚合物功能膜制备方法的研究进展[J]. 化工进展, 2021, 40(8): 4360-4370.

LIU Yi, WANG Mingwang, LYU Hongling, CHEN Jinqing. Research progress in the preparation method of covalent organic framework polymers (COFs) functional membranes[J]. Chemical Industry and Engineering Progress, 2021, 40(8): 4360-4370.

图/表 12

图1 非溶剂致相分离制备AlgDA-COF/PAN分离乙醇/水过程[8]

图2 界面聚合共混制备PA-SNW-1/PES复合膜的工艺流程[10]

图3 焙烧结晶法制备M-TpBD膜的制膜过程[20]

图4 氨基硅烷和间苯三甲醛改性氧化铝基底制备COF-LZU1/AAO复合膜[23]

图5 氨基硅烷和间苯三甲醛改性氧化铝基底制备COF-LZU1-ACOF-1双层COFs功能膜[25]

图6 多孔氧化铝基底原位溶剂热合成制备TpPa-AAO复合膜的过程[26]

图7 对苯二硼酸自缩合直接合成COF-1纳米片插层GO的2DGO/2DCOF-1复合纳米片[34]

图8 水透过超声剥离的COF-9/AAO层叠膜与GO/AAO层叠膜的比较[31]

图9 DaTp纳米片接枝插层化学剥离过程[37]

图10 多孔氧化铝盘LB提拉法制备TFP-DHF 2D COF/AAO膜及染料筛分过程[46]

图11 水相胺单体界面聚合制备Tp-Bpy薄膜[47]

图12 单向扩散法在PVDF基质膜上制备TpPa/PVDF复合膜[51]

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